Zhen Yichao, Chen Yang, Li Feng, Guo Zhenyu, Hong Zhensheng, Titirici Maria-Magdalena
Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials, College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117, China.
Fujian Provincial Collaborative Innovation Center for Advanced High-Field Superconducting Materials and Engineering, Fuzhou, 350117, China.
Proc Natl Acad Sci U S A. 2021 Oct 19;118(42). doi: 10.1073/pnas.2111119118.
Hard carbons (HCs) are a significantly promising anode material for alkali metal-ion batteries. However, long calcination time and much energy consumption are required for the traditional fabrication way, resulting in an obstacle for high-throughput synthesis and structure regulation of HCs. Herein, we report an emerging sintering method to rapidly fabricate HCs from different carbon precursors at an ultrafast heating rate (300 to 500 °C min) under one minute by a multifield-regulated spark plasma sintering (SPS) technology. HCs prepared via the SPS possess significantly fewer defects, lower porosity, and less oxygen content than those pyrolyzed in traditional sintering ways. The molecular dynamics simulations are employed to elucidate the mechanism of the remarkably accelerated pyrolysis from the quickly increased carbon sp content under the multifield effect. As a proof of concept, the SPS-derived HC exhibits an improved initial Coulombic efficiency (88.9%), a larger reversible capacity (299.4 mAh⋅g), and remarkably enhanced rate capacities (136.6 mAh⋅g at 5 A⋅g) than anode materials derived from a traditional route for Na-ion batteries.
硬碳(HCs)是一种极具前景的碱金属离子电池负极材料。然而,传统制备方法需要较长的煅烧时间和大量能耗,这给硬碳的高通量合成及结构调控带来了障碍。在此,我们报道了一种新兴的烧结方法,通过多场调控的放电等离子体烧结(SPS)技术,以超快加热速率(300至500 °C/分钟)在一分钟内由不同碳前驱体快速制备硬碳。通过SPS制备的硬碳比传统烧结方式热解得到的硬碳具有明显更少的缺陷、更低的孔隙率和更少的氧含量。利用分子动力学模拟来阐明在多场作用下碳sp含量快速增加从而显著加速热解的机理。作为概念验证,与传统方法制备的钠离子电池负极材料相比,SPS法制备的硬碳展现出更高的初始库仑效率(88.9%)、更大的可逆容量(299.4 mAh⋅g)以及显著增强的倍率性能(5 A⋅g时为136.6 mAh⋅g)。